Issue 48, 2010
From the journal:

Dalton Transactions

Proton and metal binding by cyclen-based highly rigid cryptands†

Carla Bazzicalupi,a   Andrea Bencini,*a   Samuele Ciattini,a   Franck Denat,*b   Pauline Désogère,b   Christine Goze,b   Irene Materaa  and  Barbara Valtancolia  

* Corresponding authors

a Dipartimento di Chimica Ugo Schiff, Università di Firenze, Via della Lastruccia 3, Sesto Fiorentino, Firenze, Italy
E-mail: andrea.bencini@unifi.it

b Institut de Chimie Moléculaire de l'Université de Bourgogne, UMR CNRS 5260, Université de Bourgogne, 9 avenue Alain Savary, Dijon, France
E-mail: Franck.Denat@u-bourgogne.fr

Abstract

The basicity properties of the two cryptands L1 and L2, featuring, respectively, a dibenzofuran or a diphenyl ether moiety bridging the 1,7 positions of a 1,4,7,10-tetraazacyclododecane macrocycle (cyclen) have been studied by means of potentiometric, UV-vis and fluorescence emission measurements. Both ligands show a high basicity in the first protonation step, the first basicity constant of L1 being too high to be measured in aqueous solution. The crystal structure of {[HL1]L1}+ shows that the NH2+ group is involved in an intramolecular hydrogen bonding network, which justifies the observed high basicity in solution. 1H, 13C NMR, UV-vis and fluorescence emission measurements show that, among first row divalent metal cations, both L1 and L2 selectively bind in acetonitrile Cu(II) and Zn(II), which are encapsulated within the ligand cavities. Zn(II) coordination is accompanied by a remarkable increase of the fluorescence emission of the ligands, pointing out that the molecular architecture displayed by L1 and L2 can be used to develop new OFF/ON chemosensors for this metal cation.

Graphical abstract: Proton and metal binding by cyclen-based highly rigid cryptands

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Article information

DOI
https://doi.org/10.1039/C0DT00948B
Article type
Paper
Submitted
03 Aug 2010
Accepted
15 Sep 2010
First published
04 Nov 2010

Dalton Trans., 2010,39, 11643-11653

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Proton and metal binding by cyclen-based highly rigid cryptands

C. Bazzicalupi, A. Bencini, S. Ciattini, F. Denat, P. Désogère, C. Goze, I. Matera and B. Valtancoli, Dalton Trans., 2010, 39, 11643 DOI: 10.1039/C0DT00948B

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